Zeolite SSZ-50

ABSTRACT

The present invention relates to new crystalline zeolite SSZ-50 prepared using a quaternary ammonium cation templating agent having the structure  
                 
 
     where X— is an anion which is not detrimental to the formation of the SSZ-50. SSZ-50 is useful in catalysts for hydrocarbon conversion reactions.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to crystalline zeolite SSZ-50,which has the RTH structure in accord with the Atlas for ZeoliteStructure Types. The present invention also relates to a method forpreparing crystalline zeolites having the RTH structure, includingSSZ-50, using the quaternary ammonium cation templating agentN-ethyl-N-methyl-5,7,7-trimethyl-2-azonium bicyclo[4.1.1]nonane, andprocesses employing SSZ-50 as a catalyst.

[0003] 2. State of the Art

[0004] Because of their unique sieving characteristics, as well as theircatalytic properties, crystalline molecular sieves and zeolites areespecially useful in applications such as hydrocarbon conversion, gasdrying and separation. Although many different crystalline molecularsieves have been disclosed, there is a continuing need for new zeoliteswith desirable properties for gas separation and drying, hydrocarbon andchemical conversions, and other applications. New zeolites may containnovel internal pore architectures, providing enhanced selectivities inthese processes.

SUMMARY OF THE INVENTION

[0005] In accordance with this invention, there is provided a zeolitehaving a mole ratio of about 20 or greater of an oxide selected fromsilicon oxide, germanium oxide and mixtures thereof to an oxide selectedfrom aluminum oxide, gallium oxide, iron oxide, titanium oxide, indiumoxide, vanadium oxide and mixtures thereof and having, aftercalcination, the X-ray diffraction lines of Table I below. Use of therm20 or greater means that the zeolite can be an all-silicon oxide (orgermanium oxide) material.

[0006] The present invention further provides such a zeolite having acomposition, as synthesized and in the anhydrous state, in terms of moleratios as follows: YO₂/W_(c)O_(d) 20 or greater M_(2/n)/YO₂ 0.03-0.20Q/YO₂ 0.02-0.08

[0007] wherein Y is silicon, germanium or a mixture thereof; W isaluminum, gallium, iron, titanium, indium, vanadium or mixtures thereof;c is 1 or 2; d is 2 when c is 1 (i.e., W is tetravalent) or d is 3 or 5when c is 2 (i.e., d is 3 when W is trivalent or 5 when W ispentavalent); M is an alkali metal cation, alkaline earth metal cationor mixtures thereof; n is the valence of M (i.e., 1 or 2); and Q is aquaternary ammonium cation having the structure

Template A

[0008] The zeolite has, after calcination, the X-ray diffraction linesof Table I below.

[0009] In accordance with this invention, there is also provided azeolite prepared by thermally treating a zeolite having a mole ratio ofan oxide selected from silicon oxide, germanium oxide and mixturesthereof to an oxide selected from aluminum oxide, gallium oxide, ironoxide, titanium oxide, indium oxide, vanadium oxide and mixtures thereofof about 20 or greater at a temperature of from about 200° C. to about800° C., the thus-prepared zeolite having the X-ray diffraction lines ofTable I. The present invention also includes this thus-prepared zeolitewhich is predominantly in the hydrogen form, which hydrogen form isprepared by ion exchanging with an acid or with a solution of anammonium salt followed by a second calcination.

[0010] Also provided in accordance with the present invention is amethod of preparing a crystalline material having the RTH crystalstructure and having a mole ratio of about 20 or greater of an oxideselected from silicon oxide, germanium oxide and mixtures thereof to anoxide selected from aluminum oxide, gallium oxide, iron oxide, titaniumoxide, indium oxide, vanadium oxide and mixtures thereof, said methodcomprising contacting under crystallization conditions sources of saidoxides and a templating agent comprising Template A.

[0011] The present invention additionally provides a process forconverting hydrocarbons comprising contacting a hydrocarbonaceous feedat hydrocarbon converting conditions with a catalyst comprising thezeolite of this invention. The zeolite may be predominantly in thehydrogen form. It may also be substantially free of acidity.

[0012] Further provided by the present invention is a hydrocrackingprocess comprising contacting a hydrocarbon feedstock underhydrocracking conditions with a catalyst comprising the zeolite of thisinvention, preferably predominantly in the hydrogen form.

[0013] This invention also includes a dewaxing process comprisingcontacting a hydrocarbon feedstock under dewaxing conditions with acatalyst comprising the zeolite of this invention, preferablypredominantly in the hydrogen form.

[0014] The present invention also includes a process for improving theviscosity index of a dewaxed product of waxy hydrocarbon feedscomprising contacting the waxy hydrocarbon feed under isomerizationdewaxing conditions with a catalyst comprising the zeolite of thisinvention, preferably predominantly in the hydrogen form.

[0015] The present invention further includes a process for producing aC₂₀₊ lube oil from a C₂₀₊ olefin feed comprising isomerizing said olefinfeed under isomerization conditions over a catalyst comprising at leastone Group VIII metal and the zeolite of this invention. The zeolite maybe predominantly in the hydrogen form.

[0016] In accordance with this invention, there is also provided aprocess for catalytically dewaxing a hydrocarbon oil feedstock boilingabove about 350° F. and containing straight chain and slightly branchedchain hydrocarbons comprising contacting said hydrocarbon oil feedstockin the presence of added hydrogen gas at a hydrogen pressure of about15-3000 psi with a catalyst comprising at least one Group VIII metal andthe zeolite of this invention, preferably predominantly in the hydrogenform. The catalyst may be a layered catalyst comprising a first layercomprising at least one Group VIII metal and the zeolite of thisinvention, and a second layer comprising an aluminosilicate zeolitewhich has different shape selectivity than the zeolite of said firstlayer.

[0017] Also included in the present invention is a process for preparinga lubricating oil which comprises hydrocracking in a hydrocracking zonea hydrocarbonaceous feedstock to obtain an effluent comprising ahydrocracked oil, and catalytically dewaxing said effluent comprisinghydrocracked oil at a temperature of at least about 400° F. and at apressure of from about 15 psig to about 3000 psig in the presence ofadded hydrogen gas with a catalyst comprising at least one Group VIIImetal and the zeolite of this invention. The zeolite may bepredominantly in the hydrogen form.

[0018] Further included in this invention is a process for isomerizationdewaxing a raffinate comprising contacting said raffinate in thepresence of added hydrogen with a catalyst comprising at least one GroupVIII metal and the zeolite of this invention. The raffinate may bebright stock, and the zeolite may be predominantly in the hydrogen form.

[0019] Also provided by the present invention is a catalytic crackingprocess comprising contacting a hydrocarbon feedstock in a reaction zoneunder catalytic cracking conditions in the absence of added hydrogenwith a catalyst comprising the zeolite of this invention, preferablypredominantly in the hydrogen form. Also included in this invention issuch a catalytic cracking process wherein the catalyst additionallycomprises a large pore crystalline cracking component.

[0020] The present invention further provides a process foroligomerizing olefins comprising contacting an olefin feed underoligomerization conditions with a catalyst comprising the zeolite ofthis invention.

[0021] There is further provided in accordance with this invention aprocess for isomerizing olefins comprising contacting an olefin feedunder isomerization conditions with a catalyst comprising the zeolite ofthis invention.

[0022] Further provided in accordance with this invention is a processfor the production of higher molecular weight hydrocarbons from lowermolecular weight hydrocarbons comprising the steps of:

[0023] (a) introducing into a reaction zone a lower molecular weighthydrocarbon-containing gas and contacting said gas in said zone underC₂₊ hydrocarbon synthesis conditions with a catalyst comprising thezeolite of this invention and a metal or metal compound capable ofconverting the lower molecular weight hydrocarbon to a higher molecularweight hydrocarbon; and

[0024] (b) withdrawing from said reaction zone a higher molecular weighthydrocarbon-containing stream. Preferably, the metal or metal compoundis a lanthanide or actinide metal or metal compound and the lowermolecular weight hydrocarbon is methane.

[0025] This invention also provides a process for converting loweralcohols and other oxygenated hydrocarbons comprising contacting saidlower alcohol or other oxygenated hydrocarbon with a catalyst comprisingthe zeolite of this invention under conditions to produce liquidproducts.

[0026] Also provided by the present invention is an improved process forthe reduction of oxides of nitrogen contained in a gas stream in thepresence of oxygen wherein said process comprises contacting the gasstream with a zeolite, the improvement comprising using as the zeolitethe zeolite of this invention. The zeolite may contain a metal or metalions (such as cobalt, copper or mixtures thereof) capable of catalyzingthe reduction of the oxides of nitrogen, and may be conducted in thepresence of a stoichiometric excess of oxygen. In a preferredembodiment, the gas stream is the exhaust stream of an internalcombustion engine.

[0027] Also provided in accordance with this invention is a process forthe separation of nitrogen from a nitrogen-containing gas mixturecomprising contacting the mixture with a composition comprising thezeolite of this invention. In a preferred embodiment, the gas mixturecontains nitrogen and methane.

DETAILED DESCRIPTION OF THE INVENTION

[0028] SSZ-50 is a crystalline material having the RTH crystal structureand having aluminum atoms in its crystal framework. It is believedSSZ-50 is the first such crystalline material. Other materials havingthe RTH crystal structure, such as the material designated RUB-13, areknown, but they do not have metal atoms in their crystal structure.Typically, they are prepared as silicoborates. In many cases the boronin silicoborates can be replaced with aluminum by post-synthesistreatment. However, this has not been the case with RUB-13 (see theComparative Examples below).

[0029] SSZ-50 is prepared from a reaction mixture having the compositionshown in Table A below. TABLE A Reaction Mixture YO₂/W_(a)O_(b)   15-300OH-/YO₂ 0.20-1.0 Q/YO₂ 0.10-0.40 M_(2/n)/YO₂ 0.05-0.40 H₂O/YO₂   15-50

[0030] where Y, W, Q, M and n are as defined above, and a is 1 or 2, andb is 2 when a is 1 (i.e., W is tetravalent) and b is 3 when a is 2(i.e., W is trivalent).

[0031] In practice, SSZ-50 is prepared by a process comprising:

[0032] (a) preparing an aqueous solution containing sources of at leastone oxide capable of forming a crystalline molecular sieve and TemplateA;

[0033] (b) maintaining the aqueous solution under conditions sufficientto form crystals of SSZ-50; and

[0034] (c) recovering the crystals of SSZ-50.

[0035] Typical sources of aluminum oxide for the reaction mixtureinclude aluminates, alumina, aluminum colloids, aluminum oxide coated onsilica sol, hydrated alumina gels such as Al(OH)₃ and aluminum compoundssuch as AlCl₃ and Al₂(SO₄)₃. Typical sources of silicon oxide includesilicates, silica hydrogel, silicic acid, fumed silica, colloidalsilica, tetra-alkyl orthosilicates, and silica hydroxides. Gallium,germanium, titanium, indium, vanadium and iron can be added in formscorresponding to their aluminum and silicon counterparts.

[0036] A source zeolite reagent may provide a source of aluminum. Inmost cases, the source zeolite also provides a source of silica. Thesource zeolite in its dealuminated form may also be used as a source ofsilica, with additional silicon added using, for example, theconventional sources listed above. Use of a source zeolite reagent as asource of alumina for the present process is more completely describedin U.S. Pat. No. 4,503,024 issued on Mar. 5, 1985 to Bourgogne et al.entitled “PROCESS FOR THE PREPARATION OF SYNTHETIC ZEOLITES, ANDZEOLITES OBTAINED BY SAID PROCESS”, the disclosure of which isincorporated herein by reference.

[0037] Typically, an alkali metal hydroxide and/or an alkaline earthmetal hydroxide, such as the hydroxide of sodium, potassium, lithium,cesium, rubidium, calcium, and magnesium, is used in the reactionmixture; however, this component can be omitted so long as theequivalent basicity is maintained. The templating agent may be used toprovide hydroxide ion. Thus, it may be beneficial to ion exchange, forexample, the halide for hydroxide ion, thereby reducing or eliminatingthe alkali metal hydroxide quantity required. The alkali metal cation oralkaline earth cation may be part of the as-synthesized crystallineoxide material, in order to balance valence electron charges therein.

[0038] The organic templating agent used to prepare SSZ-50 is anN-ethyl-N-methyl-5,7,7-trimethyl-2-azonium bicyclo[4.1.1]nonane cationhaving the following structure:

[0039] where X is an anion that is not detrimental to the formation ofthe SSZ-50. Representative anions include halogen, e.g., fluoride,chloride, bromide and iodide, hydroxide, acetate, sulfate,tetrafluoroborate, carboxylate, and the like. Hydroxide is the mostpreferred anion.

[0040] The reaction mixture is maintained at an elevated temperatureuntil the crystals of the SSZ-50 zeolite are formed. The hydrothermalcrystallization is usually conducted under autogenous pressure, at atemperature between 120° C. and 160° C. The crystallization period istypically greater than 1 day and preferably from about 3 days to about20 days.

[0041] Preferably, the zeolite is prepared using mild stirring oragitation.

[0042] During the hydrothermal crystallization step, the SSZ-50 crystalscan be allowed to nucleate spontaneously from the reaction mixture. Theuse of SSZ-50 crystals as seed material can be advantageous indecreasing the time necessary for complete crystallization to occur. Inaddition, seeding can lead to an increased purity of the productobtained by promoting the nucleation and/or formation of SSZ-50 over anyundesired phases. When used as seeds, SSZ-50 crystals are added in anamount between 0.1 and 10% of the weight of silica used in the reactionmixture.

[0043] Once the zeolite crystals have formed, the solid product isseparated from the reaction mixture by standard mechanical separationtechniques such as filtration. The crystals are water-washed and thendried, e.g., at 90° C. to 150° C. for from 8 to 24 hours, to obtain theas-synthesized SSZ-50 zeolite crystals. The drying step can be performedat atmospheric pressure or under vacuum.

[0044] SSZ-50 as prepared has a mole ratio of an oxide selected fromsilicon oxide, germanium oxide and mixtures thereof to an oxide selectedfrom aluminum oxide, gallium oxide, iron oxide, titanium oxide, indiumoxide, vanadium oxide and mixtures thereof of about 20 or greater; andhas, after calcination, the X-ray diffraction lines of Table I below.SSZ-50 further has a composition, as synthesized and in the anhydrousstate, in terms of mole ratios, shown in Table B below. TABLE BAs-Synthesized SSZ-50 YO₂/W_(c)O_(d) 20 or greater M_(2/n)/YO₂ 0.03-0.20Q/YO₂ 0.02-0.08

[0045] where Y, W, c, d, Q, M and n are as defined above.

[0046] Lower silica to alumina ratios may be obtained by using methodswhich insert aluminum into the crystalline framework. For example,aluminum insertion may occur by thermal treatment of the zeolite incombination with an alumina binder or dissolved source of alumina. Suchprocedures are described in U.S. Pat. No. 4,559,315, issued on Dec. 17,1985 to Chang et al.

[0047] After calcination, the SSZ-50 zeolites have a crystallinestructure whose X-ray powder diffraction pattern include thecharacteristic lines shown in Table I: TABLE I Calcined SSZ-50 2Theta^((a)) D Relative Intensity 8.45 10.5 M-VS 8.95 9.87 S-VS 10.0 8.84W-VS 17.6 5.04 W-S 18.55 4.78 W-S 22.95 3.87 W-M 24.9 3.57 W-VS 30.452.93 W-M 32.35 2.76 W 37.0 2.43 W

[0048] Table IA below shows the X-ray powder diffraction lines forcalcined SSZ-50 including actual relative intensities. TABLE IA CalcinedSSZ-50 2 Theta^((a)) D Relative Intensity (I/I₀ × 100) 8.45 10.5 35-1008.95 9.87 40-100 10.0 8.84 10-80  17.6 5.04 10-60  18.55 4.78 5-60 22.953.87 5-25 24.9 3.57 5-75 30.45 2.93 5-25 32.35 2.76 5-15 37.0 2.43 1-10

[0049] The X-ray powder diffraction patterns were determined by standardtechniques. The radiation was the K-alpha/doublet of copper. The peakheights and the positions, as a function of 2θ where θ is the Braggangle, were read from the relative intensities of the peaks, and d, theinterplanar spacing in Angstroms corresponding to the recorded lines,can be calculated.

[0050] Representative peaks from the X-ray diffraction pattern ofcalcined SSZ-50 are shown in Table I. Calcination can result in changesin the intensities of the peaks as compared to patterns of the “as-made”material, as well as minor shifts in the diffraction pattern. Thezeolite produced by exchanging the metal or other cations present in thezeolite with various other cations (such as H⁺ or NH₄ ⁺) yieldsessentially the same diffraction pattern, although again, there may beminor shifts in the interplanar spacing and variations in the relativeintensities of the peaks. Notwithstanding these minor perturbations, thebasic crystal lattice remains unchanged by these treatments.

[0051] Crystalline SSZ-50 can be used as-synthesized, but preferablywill be thermally treated (calcined). Usually, it is desirable to removethe alkali metal cation by ion exchange and replace it with hydrogen,ammonium, or any desired metal ion. The zeolite can be leached withchelating agents, e.g., EDTA or dilute acid solutions, to increase thesilica to alumina mole ratio. The zeolite can also be steamed; steaminghelps stabilize the crystalline lattice to attack from acids.

[0052] The zeolite can be used in intimate combination withhydrogenating components, such as tungsten, vanadium molybdenum,rhenium, nickel cobalt, chromium, manganese, or a noble metal, such aspalladium or platinum, for those applications in which ahydrogenation-dehydrogenation function is desired.

[0053] Metals may also be introduced into the zeolite by replacing someof the cations in the zeolite with metal cations via standard ionexchange techniques (see, for example, U.S. Pat. No. 3,140,249 issuedJul. 7, 1964 to Plank et al.; U.S. Pat. No. 3,140,251 issued Jul. 7,1964 to Plank et al.; and U.S. Pat. No. 3,140,253 issued Jul. 7, 1964 toPlank et al.). Typical replacing cations can include metal cations,e.g., rare earth, Group IA, Group IIA and Group VIII metals, as well astheir mixtures. Of the replacing metallic cations, cations of metalssuch as rare earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, andFe are particularly preferred.

[0054] The hydrogen, ammonium, and metal components can be ion-exchangedinto the SSZ-50. The zeolite can also be impregnated with the metals,or, the metals can be physically and intimately admixed with the zeoliteusing standard methods known to the art.

[0055] Typical ion-exchange techniques involve contacting the syntheticzeolite with a solution containing a salt of the desired replacingcation or cations. Although a wide variety of salts can be employed,chlorides and other halides, acetates, nitrates, and sulfates areparticularly preferred. The zeolite is usually calcined prior to theion-exchange procedure to remove the organic matter present in thechannels and on the surface, since this results in a more effective ionexchange. Representative ion exchange techniques are disclosed in a widevariety of patents including U.S. Pat. No. 3,140,249 issued on Jul. 7,1964 to Plank et al.; U.S. Pat. No. 3,140,251 issued on Jul. 7, 1964 toPlank et al.; and U.S. Pat. No. 3,140,253 issued on Jul. 7, 1964 toPlank et al.

[0056] Following contact with the salt solution of the desired replacingcation, the zeolite is typically washed with water and dried attemperatures ranging from 65° C. to about 200° C. After washing, thezeolite can be calcined in air or inert gas at temperatures ranging fromabout 200° C. to about 800° C. for periods of time ranging from 1 to 48hours, or more, to produce a catalytically active product especiallyuseful in hydrocarbon conversion processes.

[0057] Regardless of the cations present in the synthesized form ofSSZ-50, the spatial arrangement of the atoms which form the basiccrystal lattice of the zeolite remains essentially unchanged.

[0058] SSZ-50 can be formed into a wide variety of physical shapes.Generally speaking, the zeolite can be in the form of a powder, agranule, or a molded product, such as extrudate having a particle sizesufficient to pass through a 2-mesh (Tyler) screen and be retained on a400-mesh (Tyler) screen. In cases where the catalyst is molded, such asby extrusion with an organic binder, the aluminosilicate can be extrudedbefore drying, or, dried or partially dried and then extruded.

[0059] SSZ-50 can be composited with other materials resistant to thetemperatures and other conditions employed in organic conversionprocesses. Such matrix materials include active and inactive materialsand synthetic or naturally occurring zeolites as well as inorganicmaterials such as clays, silica and metal oxides. Examples of suchmaterials and the manner in which they can be used are disclosed in U.S.Pat. No. 4,910,006, issued May 20, 1990 to Zones et al., and U.S. Pat.No. 5,316,753, issued May 31, 1994 to Nakagawa, both of which areincorporated by reference herein in their entirety.

Hydrocarbon Conversion Processes

[0060] SSZ-50 zeolites are useful in hydrocarbon conversion reactions.Hydrocarbon conversion reactions are chemical and catalytic processes inwhich carbon containing compounds are changed to different carboncontaining compounds. Examples of hydrocarbon conversion reactions inwhich SSZ-50 are expected to be useful include hydrocracking, dewaxing,catalytic cracking and olefin formation reactions. The catalysts arealso expected to be useful in other petroleum refining and hydrocarbonconversion reactions such as isomerizing n-paraffins and naphthenes,isomerizing olefins, polymerizing and oligomerizing olefinic oracetylenic compounds such as isobutylene and butene-1, reforming,forming higher molecular weight hydrocarbons from lower molecular weighthydrocarbons (e.g., methane upgrading) and oxidation reactions. TheSSZ-50 catalysts may have high selectivity, and under hydrocarbonconversion conditions can provide a high percentage of desired productsrelative to total products.

[0061] SSZ-50 zeolites can be used in processing hydrocarbonaceousfeedstocks. Hydrocarbonaceous feedstocks contain carbon compounds andcan be from many different sources, such as virgin petroleum fractions,recycle petroleum fractions, shale oil, liquefied coal, tar sand oil,synthetic paraffins from NAO, recycled plastic feedstocks and, ingeneral, can be any carbon containing feedstock susceptible to zeoliticcatalytic reactions. Depending on the type of processing thehydrocarbonaceous feed is to undergo, the feed can contain metal or befree of metals, it can also have high or low nitrogen or sulfurimpurities. It can be appreciated, however, that in general processingwill be more efficient (and the catalyst more active) the lower themetal, nitrogen, and sulfur content of the feedstock.

[0062] The conversion of hydrocarbonaceous feeds can take place in anyconvenient mode, for example, in fluidized bed, moving bed, or fixed bedreactors depending on the types of process desired. The formulation ofthe catalyst particles will vary depending on the conversion process andmethod of operation.

[0063] Other reactions which can be performed using the catalyst of thisinvention containing a metal, e.g., a Group VIII metal such platinum,include hydrogenation-dehydrogenation reactions, denitrogenation anddesulfurization reactions.

[0064] The following table indicates typical reaction conditions whichmay be employed when using catalysts comprising SSZ-50 in thehydrocarbon conversion reactions of this invention. Preferred conditionsare indicated in parentheses. Process Temp.,° C. Pressure LHSVHydrocracking 175-485 0.5-350 bar 0.1-30 Dewaxing 200-475  15-3000 psig0.1-20 (250-450) (200-3000) (0.2-10) Cat. cracking 127-885 subatm.-¹0.5-50 (atm.-5 atm.) Oligomerization  232-649² 0.1-50 atm.^(2,3) 0.2-50²   10-232⁴ —  0.05-20⁵    (27-204)⁴ —  (0.1-10)⁵ Condensation of260-538 0.5-1000 psig  0.5-50⁵ alcohols Isomerization  93-538  50-1000psig   1-10 (204-315)  (1-4)

[0065] Other reaction conditions and parameters are provided below.

Hydrocracking

[0066] Using a catalyst which comprises SSZ-50, preferably predominantlyin the hydrogen form, and a hydrogenation promoter, heavy petroleumresidual feedstocks, cyclic stocks and other hydrocrackate charge stockscan be hydrocracked using the process conditions and catalyst componentsdisclosed in the aforementioned U.S. Pat. No. 4,910,006 and U.S. Pat.No. 5,316,753.

[0067] The hydrocracking catalysts contain an effective amount of atleast one hydrogenation component of the type commonly employed inhydrocracking catalysts. The hydrogenation component is generallyselected from the group of hydrogenation catalysts consisting of one ormore metals of Group VIB and Group VIII, including the salts, complexesand solutions containing such. The hydrogenation catalyst is preferablyselected from the group of metals, salts and complexes thereof of thegroup consisting of at least one of platinum, palladium, rhodium,iridium, ruthenium and mixtures thereof or the group consisting of atleast one of nickel, molybdenum, cobalt, tungsten, titanium, chromiumand mixtures thereof. Reference to the catalytically active metal ormetals is intended to encompass such metal or metals in the elementalstate or in some form such as an oxide, sulfide, halide, carboxylate andthe like. The hydrogenation catalyst is present in an effective amountto provide the hydrogenation function of the hydrocracking catalyst, andpreferably in the range of from 0.05 to 25% by weight.

Dewaxing

[0068] SSZ-50, preferably predominantly in the hydrogen form, can beused to dewax hydrocarbonaceous feeds by selectively removing straightchain paraffins. Typically, the viscosity index of the dewaxed productis improved (compared to the waxy feed) when the waxy feed is contactedwith SSZ-50 under isomerization dewaxing conditions.

[0069] The catalytic dewaxing conditions are dependent in large measureon the feed used and upon the desired pour point. Hydrogen is preferablypresent in the reaction zone during the catalytic dewaxing process. Thehydrogen to feed ratio is typically between about 500 and about 30,000SCF/bbl (standard cubic feet per barrel), preferably about 1000 to about20,000 SCF/bbl. Generally, hydrogen will be separated from the productand recycled to the reaction zone. Typical feedstocks include light gasoil, heavy gas oils and reduced crudes boiling above about 350° F.

[0070] A typical dewaxing process is the catalytic dewaxing of ahydrocarbon oil feedstock boiling above about 350° F. and containingstraight chain and slightly branched chain hydrocarbons by contactingthe hydrocarbon oil feedstock in the presence of added hydrogen gas at ahydrogen pressure of about 15-3000 psi with a catalyst comprising SSZ-50and at least one Group VIII metal.

[0071] The SSZ-50 hydrodewaxing catalyst may optionally contain ahydrogenation component of the type commonly employed in dewaxingcatalysts. See the aforementioned U.S. Pat. No. 4,910,006 and U.S. Pat.No. 5,316,753 for examples of these hydrogenation components.

[0072] The hydrogenation component is present in an effective amount toprovide an effective hydrodewaxing and hydroisomerization catalystpreferably in the range of from about 0.05 to 5% by weight. The catalystmay be run in such a mode to increase isodewaxing at the expense ofcracking reactions.

[0073] The feed may be hydrocracked, followed by dewaxing. This type oftwo stage process and typical hydrocracking conditions are described inU.S. Pat. No. 4,921,594, issued May 1, 1990 to Miller, which isincorporated herein by reference in its entirety.

[0074] SSZ-50 may also be utilized as a dewaxing catalyst in the form ofa layered catalyst. That is, the catalyst comprises a first layercomprising zeolite SSZ-50 and at least one Group VIII metal, and asecond layer comprising an aluminosilicate zeolite which has differentshape selectivity than zeolite SSZ-50. The use of layered catalysts isdisclosed in U.S. Pat. No. 5,149,421, issued Sep. 22, 1992 to Miller,which is incorporated by reference herein in its entirety. The layeringmay also include a bed of SSZ-50 layered with a non-zeolitic componentdesigned for either hydrocracking or hydrofinishing.

[0075] SSZ-50 may also be used to dewax raffinates, including brightstock, under conditions such as those disclosed in U.S. Pat. No.4,181,598, issued Jan. 1, 1980 to Gillespie et al., which isincorporated by reference herein in its entirety.

[0076] It is often desirable to use mild hydrogenation (sometimesreferred to as hydrofinishing) to produce more stable dewaxed products.The hydrofinishing step can be performed either before or after thedewaxing step, and preferably after. Hydrofinishing is typicallyconducted at temperatures ranging from about 190° C. to about 340° C. atpressures from about 400 psig to about 3000 psig at space velocities(LHSV) between about 0.1 and 20 and a hydrogen recycle rate of about 400to 1500 SCF/bbl. The hydrogenation catalyst employed must be activeenough not only to hydrogenate the olefins, diolefins and color bodieswhich may be present, but also to reduce the aromatic content. Suitablehydrogenation catalyst are disclosed in U.S. Pat. No. 4,921,594, issuedMay 1, 1990 to Miller, which is incorporated by reference herein in itsentirety. The hydrofinishing step is beneficial in preparing anacceptably stable product (e.g., a lubricating oil) since dewaxedproducts prepared from hydrocracked stocks tend to be unstable to airand light and tend to form sludges spontaneously and quickly.

[0077] Lube oil may be prepared using SSZ-50. For example, a C₂₀₊ lubeoil may be made by isomerizing a C₂₀₊ olefin feed over a catalystcomprising SSZ-50 in the hydrogen form and at least one Group VIIImetal. Alternatively, the lubricating oil may be made by hydrocrackingin a hydrocracking zone a hydrocarbonaceous feedstock to obtain aneffluent comprising a hydrocracked oil, and catalytically dewaxing theeffluent at a temperature of at least about 400° F. and at a pressure offrom about 15 psig to about 3000 psig in the presence of added hydrogengas with a catalyst comprising SSZ-50 in the hydrogen form and at leastone Group VIII metal.

Catalytic Cracking

[0078] Hydrocarbon cracking stocks can be catalytically cracked in theabsence of hydrogen using SSZ-50, preferably predominantly in thehydrogen form.

[0079] When SSZ-50 is used as a catalytic cracking catalyst in theabsence of hydrogen, the catalyst may be employed in conjunction withtraditional cracking catalysts, e.g., any aluminosilicate heretoforeemployed as a component in cracking catalysts. Typically, these arelarge pore, crystalline aluminosilicates. Examples of these traditionalcracking catalysts are disclosed in the aforementioned U.S. Pat. No.4,910,006 and U.S. Pat. No. 5,316,753. When a traditional crackingcatalyst (TC) component is employed, the relative weight ratio of the TCto the SSZ-50 is generally between about 1:10 and about 500:1, desirablybetween about 1:10 and about 200:1, preferably between about 1:2 andabout 50:1, and most preferably is between about 1:1 and about 20:1. Thenovel zeolite and/or the traditional cracking component may be furtherion exchanged with rare earth ions to modify selectivity.

[0080] The cracking catalysts are typically employed with an inorganicoxide matrix component. See the aforementioned U.S. Pat. No. 4,910,006and U.S. Pat. No. 5,316,753 for examples of such matrix components.

Oligomerization

[0081] It is expected that SSZ-50 can also be used to oligomerizestraight and branched chain olefins having from about 2 to 21 andpreferably 2-5 carbon atoms. The oligomers which are the products of theprocess are medium to heavy olefins which are useful for both fuels,i.e., gasoline or a gasoline blending stock and chemicals.

[0082] The oligomerization process comprises contacting the olefinfeedstock in the gaseous or liquid phase with a catalyst comprisingSSZ-50.

[0083] The zeolite can have the original cations associated therewithreplaced by a wide variety of other cations according to techniques wellknown in the art. Typical cations would include hydrogen, ammonium andmetal cations including mixtures of the same. Of the replacing metalliccations, particular preference is given to cations of metals such asrare earth metals, manganese, calcium, as well as metals of Group II ofthe Periodic Table, e.g., zinc, and Group VIII of the Periodic Table,e.g., nickel. One of the prime requisites is that the zeolite have afairly low aromatization activity, i.e., in which the amount ofaromatics produced is not more than about 20% by weight. This isaccomplished by using a zeolite with controlled acid activity [alphavalue] of from about 0.1 to about 120, preferably from about 0.1 toabout 100, as measured by its ability to crack n-hexane.

[0084] Alpha values are defined by a standard test known in the art,e.g., as shown in U.S. Pat. No. 3,960,978 issued on Jun. 1, 1976 toGivens et al. which is incorporated totally herein by reference. Ifrequired, such zeolites may be obtained by steaming, by use in aconversion process or by any other method which may occur to one skilledin this art.

Isomerization of Olefins

[0085] SSZ-50 can be used to isomerize olefins. The feed stream is ahydrocarbon stream containing at least one C₄₋₆ olefin, preferably aC₄₋₆ normal olefin, more preferably normal butene. Normal butene as usedin this specification means all forms of normal butene, e.g., 1-butene,cis-2-butene, and trans-2-butene. Typically, hydrocarbons other thannormal butene or other C₄₋₆ normal olefins will be present in the feedstream. These other hydrocarbons may include, e.g., alkanes, otherolefins, aromatics, hydrogen, and inert gases.

[0086] The feed stream typically may be the effluent from a fluidcatalytic cracking unit or a methyl-tert-butyl ether unit. A fluidcatalytic cracking unit effluent typically contains about 40-60 weightpercent normal butenes. A methyl-tert-butyl ether unit effluenttypically contains 40-100 weight percent normal butene. The feed streampreferably contains at least about 40 weight percent normal butene, morepreferably at least about 65 weight percent normal butene. The termsiso-olefin and methyl branched iso-olefin may be used interchangeably inthis specification.

[0087] The process is carried out under isomerization conditions. Thehydrocarbon feed is contacted in a vapor phase with a catalystcomprising the SSZ-50. The process may be carried out generally at atemperature from about 625° F. to about 950° F. (329-510° C.), forbutenes, preferably from about 700° F. to about 900° F. (371-482° C.),and about 350° F. to about 650° F. (177-343° C.) for pentenes andhexenes. The pressure ranges from subatmospheric to about 200 psig,preferably from about 15 psig to about 200 psig, and more preferablyfrom about 1 psig to about 150 psig.

[0088] The liquid hourly space velocity during contacting is generallyfrom about 0.1 to about 50 hr⁻¹, based on the hydrocarbon feed,preferably from about 0.1 to about 20 hr⁻¹, more preferably from about0.2 to about 10 hr⁻¹, most preferably from about 1 to about 5 hr⁻¹. Ahydrogen/hydrocarbon molar ratio is maintained from about 0 to about 30or higher. The hydrogen can be added directly to the feed stream ordirectly to the isomerization zone. The reaction is preferablysubstantially free of water, typically less than about two weightpercent based on the feed. The process can be carried out in a packedbed reactor, a fixed bed, fluidized bed reactor, or a moving bedreactor. The bed of the catalyst can move upward or downward. The molepercent conversion of, e.g., normal butene to iso-butene is at least 10,preferably at least 25, and more preferably at least 35.

Methane Upgrading

[0089] Higher molecular weight hydrocarbons can be formed from lowermolecular weight hydrocarbons by contacting the lower molecular weighthydrocarbon with a catalyst comprising SSZ-50 and a metal or metalcompound capable of converting the lower molecular weight hydrocarbon toa higher molecular weight hydrocarbon. Examples of such reactionsinclude the conversion of methane to C₂+hydrocarbons such as ethylene orbenzene or both. Examples of useful metals and metal compounds includelanthanide and or actinide metals or metal compounds.

[0090] These reactions, the metals or metal compounds employed and theconditions under which they can be run are disclosed in U.S. Pat. No.4,734,537, issued Mar. 29, 1988 to Devries et al.; U.S. Pat. No.4,939,311, issued Jul. 3, 1990 to Washecheck et al.; U.S. Pat. No.4,962,261, issued Oct. 9, 1990 to Abrevaya et al.; U.S. Pat. No.5,095,161, issued Mar. 10, 1992 to Abrevaya et al.; U.S. Pat. No.5,105,044, issued Apr. 14, 1992 to Han et al.; U.S. Pat. No. 5,105,046,issued Apr. 14, 1992 to Washecheck; U.S. Pat. No. 5,238,898, issued Aug.24, 1993 to Han et al.; U.S. Pat. No. 5,321,185, issued Jun. 14, 1994 tovan der Vaart; and U.S. Pat. No. 5,336,825, issued Aug. 9, 1994 toChoudhary et al., each of which is incorporated herein by reference inits entirety.

Condensation of Alcohols

[0091] SSZ-50 can be used to convert lower aliphatic alcohols having 1to 10 carbon atoms to olefins. The process disclosed in U.S. Pat. No.3,894,107, issued Jul. 8, 1975 to Butter et al., describes the processconditions used in this process, which patent is incorporated totallyherein by reference.

[0092] The catalyst may be in the hydrogen form or may be base exchangedor impregnated to contain ammonium or a metal cation complement,preferably in the range of from about 0.05 to 5% by weight. The metalcations that may be present include any of the metals of the Groups Ithrough VIII of the Periodic Table. However, in the case of Group IAmetals, the cation content should in no case be so large as toeffectively inactivate the catalyst, nor should the exchange be such asto eliminate all acidity. There may be other processes involvingtreatment of oxygenated substrates where a basic catalyst is desired.

Other Uses for SSZ-50

[0093] SSZ-50 can also be used as an adsorbent with high selectivitiesbased on molecular sieve behavior and also based upon preferentialhydrocarbon packing within the pores.

[0094] SSZ-50 may also be used for the catalytic reduction of the oxidesof nitrogen in a gas stream. Typically, the gas stream also containsoxygen, often a stoichiometric excess thereof. Also, the SSZ-50 maycontain a metal or metal ions within or on it which are capable ofcatalyzing the reduction of the nitrogen oxides. Examples of such metalsor metal ions include copper, cobalt and mixtures thereof.

[0095] One example of such a process for the catalytic reduction ofoxides of nitrogen in the presence of a zeolite is disclosed in U.S.Pat. No. 4,297,328, issued Oct. 27, 1981 to Ritscher et al., which isincorporated by reference herein. There, the catalytic process is thecombustion of carbon monoxide and hydrocarbons and the catalyticreduction of the oxides of nitrogen contained in a gas stream, such asthe exhaust gas from an internal combustion engine. The zeolite used ismetal ion-exchanged, doped or loaded sufficiently so as to provide aneffective amount of catalytic copper metal or copper ions within or onthe zeolite. In addition, the process is conducted in an excess ofoxidant, e.g., oxygen.

[0096] SSZ-50 may also be used in the separation of gases, such as theseparation of nitrogen from a nitrogen-containing gas mixture. Oneexample of such separation is the separation of nitrogen from methane(e.g., the separation of nitrogen from natural gas).

EXAMPLES

[0097] The following examples demonstrate but do not limit the presentinvention.

Example 1 Synthesis of N-ethyl-N-methyl-5,7,7-trimethyl-2-azoniumbicyclo[4.1.1]nonane cation (Template A)

[0098] 20 Grams of verbenone (Aldrich) is hydrogenated in a Parrhydrogenator to reduce the olefin. 2 Grams of Pd on charcoal is used ascatalyst in 200 cc ethanol (100%) and under 60 psig of hydrogen. Afterreaction, the mixture is passed through a short column of celite onsilica, using ethanol for rinsing. Repeating this process yieldsadditional quantities of the reduced bicyclo ketone. 72.9 Grams of thisproduct is then combined with 40.34 grams of hydroxylaminehydrochloride, 78.6 grams of sodium acetate (tri-hydrate), 435 ml ofethanol (95%), and 218 grams of water. This mixture is refluxed for 2hours. The cooled mixture is worked up by pouring into a brine solutionand carrying out chloroform extractions (3×250 ml). The extracts aredried and stripped. Next, 88 grams of this oxime is reacted with severalcomponents to yield a Beckmann rearranged product. The oxime is refluxedfor 6 hours (80° C.) in a mixture of 153 grams of tosyl chloride, 185grams of potassium carbonate, 768 ml of dimethoxy ethane, and 666 ml ofwater. The dimethoxy ethane is removed in a roto-evaporator. Theremaining aqueous phase is extracted with chloroform (3×250 ml), and thelatter is washed once with 300 ml of brine solution and then dried oversodium sulfate. Removing the dried solvent yields 76 grams of oil, amixture of lactam products.

[0099] The desired product can be isolated by column separation using 2kg of silica, slurried in n-hexane. The oil is loaded onto the columnusing 50 ml of methylene chloride. The column is run using 2% methanolin chloroform. 57.55 Grams of product is collected from fractions withthe same TLC.

[0100] For reduction of the lactam, the following equipment is set up: a3-neck round bottom with a cooling condenser, an addition funnel and agas bubbler. A dry ice/acetone cold bath was used to control temperatureduring the reduction step. Under an inert atmosphere, 41.2 grams oflithium aluminum hydride is added into 1030 ml anhydrous diethyl ether(cooled). Using the addition funnel, 57.5 grams of lactam is added in520 ml methylene chloride. The addition is intentionally slow to controlheat evolution. Gradually, the reaction is allowed to come to roomtemperature. Following by TLC shows the reaction is complete afterovernight stirring at room temperature. Carefully, 41 ml of water isadded with good stirring, and considerable gas evolution is seen via thebubbler. Next, 41 grams of 15% NaOH is slowly added, and then finally123.5 ml of water is added last and stirred for a while. The solidsformed are collected by filtration and washed with additional methylenechloride. The combined organic washings are treated with an acidicaqueous solution to extract the protonated amines. Next, the aqueoussolution is made basic and extracted with ether to collect the freeamine.

[0101] 12.80 Grams of the resulting amine is placed in an Erlenmeyerflask equipped with condenser. 80 Milliliters of methanol is used assolvent and 19.12 grams of ethyl iodide is the alkylating agent. Thereaction mixture is refluxed for 48 hours. The salt product is forcedout with ether addition. The oil is taken up in 100 ml water, pH isadjusted to12 and the free amine is extracted into methylene chloride.After drying and stripping, 11.14 grams of mono ethylated amine isrecovered as an oil. This material is reacted in 60 ml of methanol with17.56 grams of methyl iodide to give the desired N, methyl, ethylquaternized product, Template A. Recrystallization from a solvent systemconsisting of the mixture of acetone, ethyl acetate and ether gives asolid with a melting point in the 215-220 range. The C and H NMR arecorrect for the desired product. The template is converted from theiodide form to the hydroxide form using BioRad AG 1-X8 exchange resin.

Example 2 Synthesis of SSZ-50

[0102] 3.13 Grams of a 0.48 M solution of Template A is placed into theTeflon cup of a Parr 23 ml reactor. 0.95 Grams of 1.0 N NaOH is addedalong with 1.07 grams of water. Solid SiO2 is added as 0.533 grams ofCabosil, and aluminum is supplied as 0.17 grams of sodium Y zeolite. Themixture is heated at 160° C. with 43 RPM tumbling within a Blue M oven.The reaction is stopped after 7 days. The cooled reaction product has apH near 12.5. Electron micrographs show the presence of a newcrystalline product. The solids are filtered, washed, dried, anddetermined by X-ray diffraction to be SSZ-50.

Example 3 Synthesis of SSZ-50

[0103] A reaction like Example 2 is set up except that the aluminumsource is LZ 210, a partially dealuminated Y zeolite. 0.19 Grams of thiscomponent is mixed with 4.18 grams of the same template solution, 0.51grams of the NaOH solution, 0.14 grams of water and 0.49 grams ofCabosil. Heating at 170° C. for 9 days produced the SSZ-50 product. Thefull XRD pattern is shown in Table II below. TABLE II 2 Theta^((a)) DI/I₀ × 100 8.48 10.42 55 8.97 9.85 100 10.02 8.22 23 12.31 7.18 5 14.096.28 10 15.68 5.65 12 17.62 5.03 40 18.57 4.77 63 19.37 4.58 34 19.484.55 36 19.90 4.46 56 20.13 sh 4.41 32 21.26 4.18 2 22.90 3.88 17 23.25sh 3.82 8 24.93 3.57 59 25.25 sh 3.52 36 25.85 3.44 7 27.18 3.28 7 27.933.19 10 28.13 sh 3.17 8 28.32 sh 3.15 7 28.54 3.13 8 29.93 2.98 7 30.36sh 2.94 12 30.47 2.93 13 31.25 sh 2.86 5 31.50 2.84 7 32.38 2.76 1233.05 2.71 3 33.56 2.67 4 35.21 2.55 4 35.69 2.51 2 37.01 2.43 5 37.712.39 3 39.15 2.30 3 41.09 2.20 3

Example 4 Synthesis of High-Silica SSZ-50

[0104] SSZ-50 can be synthesized from a mixture starting with asilica/alumina mole ratio of 100. 3.13 Grams of template, 1.0 gram of 1N NaOH and 3.78 grams of water are combined. An aluminum source, 0.02grams of Reheis F-2000 (53% Al2O3) is dissolved in the reaction mixtureand 0.62 grams of Cabosil is added last. The reaction vessel is closedand heated at 170° C. with 43 RPM tumbling. After 16 days of heating thereaction has transformed from a gel to a settled set of solids below aclear solution. The typical work-up yields a product which is SSZ-50 byXRD analysis.

Example 5 Calcination of SSZ-50

[0105] The SSZ-50 made in Example 3 is calcined using a ramp program: 2degrees C./min to 125° C., hold for 2 hours, then 2 degrees C./min to540° C., hold for 4 hours. The recovered material is analyzed by XRD andshows that SSZ-50 retains crystallinity. The full XRD pattern is shownin Table III below. TABLE III 2 Theta^((a)) D I/I₀ × 100 8.46 10.44 798.94 9.88 100 10.00 8.84 47 12.37 7.15 4 12.73 6.95 3 14.11 6.27 2 15.685.65 3 17.03 5.20 1 17.59 5.04 9 18.62 4.76 27 19.36 4.58 11 19.75 4.4912 19.93 4.45 16 20.14 4.41 10 21.27 4.17 2 23.00 3.86 10 24.93 3.57 1125.40 sh 3.50 6 25.75 sh 3.46 4 27.26 3.27 2 27.94 3.19 4 28.50 3.13 229.83 2.99 3 30.48 2.93 7 31.25 2.86 1 31.58 2.83 3 32.36 2.76 5 33.722.66 2 34.73 sh 2.58 1 35.23 2.55 2 37.03 2.43 2 37.77 2.38 1

Example 6 N₂ Micropore Volume of SSZ-50

[0106] Calcined SSZ-50, after drying to 350° C., in situ, is measuredfor nitrogen gas uptake. The void volume capacity is found to be 0.22cc/gm with a surface area measured to 500 m²/gm. This demonstrates thatSSZ-50 is highly microporous

Example 7 Use of SSZ-50 to Convert Methanol

[0107] The calcined material from Example 5 is given one NH4NO3 exchangeat 90° C. for 2 hours and then pelleted and meshed to 20-40. The chips,0.37 grams, are loaded into a downflow reactor. The chips are supportedby packed glass wool in the reactor. Using a Harvard syringe pump,methanol is delivered to the catalyst bed, once it has been dried atabout 430° C. The reaction of methanol is carried out under atmosphericconditions using 200 cc/min N2 sweep. The actual reaction was carriedout at 400° C., using a feed of 22.1% methanol in water.

[0108] The products from the reaction are shown below. There is nomethanol breakthrough for almost the first 5 hours which is verysurprising for a small pore zeolite like SSZ-50. The catalyst makeslight products of chiefly C₄ and lower. Impressive is the fact that theproducts are greater than 95% olefinic. Run time (min.) 10 80 150 220290 360 430 465 Methane 0.68 0.47 0.45 0.58 0.66 0.5 0.53 0.62 Ethylene17.79 22.55 17.3 19.69 23.62 20.51 19.44 19.49 Propylene/C₄ 51.87 51.3349.68 48.93 47.29 44.98 39.24 38.54 Dimethylether 0.47 1.48 2.12 2.46Isobutane 2.54 Methanol 1.16 4.77 14.97 15.5 C₄ 8.17 1.07 0.85 0.64 C₄ =12.39 19.49 24.17 26.48 21.29 21.37 18.61 18.31 C₅ = 6.51 5.09 7.55 6.685.51 6.51 5.07 5.08 Olefin* 88.56 98.46 98.7 98.78 97.71 93.37 82.3681.42 Paraffin 11.39 1.54 1.3 1.22 0.66 0.5 0.53 0.62 Olefin/Paraffin7.78 63.94 75.92 80.97 148.05 186.74 155.4 1312.32

Example 8 Synthesis of All-Silica SSZ-50

[0109] Five millimoles of Template A in 9 grams of solution is mixedwith 2.10 grams of tetraethyl orthosilicate in a Teflon cup and theresulting mixture is allowed to hydrolyyse the silica and let ethanolevaporate at room temperature until the net mass in the Teflon cup is4.00 grams. This requires several days. Then 0.205 gram of 50% HF isadded carefully and dropwise to the Teflon cup. The resulting mixture isstirred with a plastic spatula until a thick gel forms. The reactor isclosed, loaded onto a spit (43 rpm) and heated to 150° C. whiletumbling. The reactor is checked periodically for signs of liquidseparation (an indication of the gel transformation into crystals).After 29 days of reaction, the solids that have formed are collected,filtered and washed. X-ray powder diffraction shows the product to beSSZ-50.

Comparative Example A Synthesis of Borosilicate Having RTH Structure

[0110] SSZ-50 is structurally related to zeolite RUB-13, a borosilicate.Template A can also crystallize this product. 4.18 Grams of Template Ais mixed in the Teflon cup of a Parr reactor with 0.80 grams of 1 NNaOH, 3.0 grams of water and 0.038 grams of sodium borate decahydrate.When the borate salt had dissolved, 0.62 grams of Cabosil is blended inand reaction is commenced with 160° C. heating and 43 RPM tumbling. Thecrystallization is complete by 16 days of run time. The product had theRUB-13 XRD pattern.

[0111] The RUB-13 product is calcined as in Example 6, except theatmosphere is largely nitrogen with only a minor “bleed” of air beingadmitted into the sweep gas. The calcined RUB-13 also is found to have alarge micropore volume, 0.22 cc/gm.

Comparative Example B Aluminum Treatment of Borosilicate RUB-13

[0112] An attempt was made to replace the boron in the borosilicateRUB-13 of Comparative Example A with aluminum. 0.62 Grams of calcinedRUB-13 from Comparative example A is heated overnight to 86° C. in 16 mlwater containing 6 grams of aluminum nitrate nonahydrate. The treatedproduct is filtered, washed with 100 ml of 0.01 N HCl and then water.The product is dried and prepared for catalyst evaluation as describedin Example 7.

Comparative Example C Methanol Conversion

[0113] Conversion of methanol is attempted as described above in Example7 using the RUB-13 product from Comparative Example B. No conversion ofthe methanol is observed. This indicates that one could not get anactive methanol conversion catalyst of the RTH structure starting withRUB-13. The recovered RUB-13 is white (no coke formation) and issubsequently analyzed for micropore volume to ensure that no poreplugging has occurred during the aluminum treatment. The inactivecatalyst measured a micropore volume of 0.22 cc/gm, the value expectedfor a completely open RTH zeolite.

What is claimed is:
 1. A zeolite having a mole ratio of about 20 orgreater of an oxide selected from the group consisting of silicon oxide,germanium oxide and mixtures thereof to an oxide selected from aluminumoxide, gallium oxide, iron oxide, titanium oxide, indium oxide, vanadiumoxide and mixtures thereof, and having, after calcination, the X-raydiffraction lines of Table I.
 2. A zeolite according to claim 1 whereinthe oxides comprise silicon oxide and aluminum oxide.
 3. A zeoliteaccording to claim 1 wherein said zeolite is predominantly in thehydrogen form.
 4. A zeolite according to claim 1 wherein said zeolite issubstantially free of acidity.
 5. A zeolite having a composition, assynthesized and in the anhydrous state, in terms of mole ratios asfollows: YO₂/W_(c)O_(d) 20 or greater M_(2/n)/YO₂ 0.03-0.20 Q/YO₂0.02-0.08

wherein Y is silicon, germanium or a mixture thereof; W is aluminum,gallium, iron, titanium, indium, vanadium or mixtures thereof, c is 1 or2; d is 2 when c is 1 or d is 3 or 5 when c is 2; M is an alkali metalcation, alkaline earth metal cation or mixtures thereof; n is thevalence of M; and Q is a quaternary ammonium cation having the structure

where X— is an anion which is not detrimental to the formation of thezeolite.
 6. A zeolite according to claim 5 wherein W is aluminum and Yis silicon.
 7. A method of preparing a crystalline material having theRTH crystal structure and having a mole ratio of about 20 or greater ofan oxide selected from silicon oxide, germanium oxide and mixturesthereof to an oxide selected from aluminum oxide, gallium oxide, ironoxide, titanium oxide, indium oxide, vanadium oxide and mixturesthereof, said method comprising contacting under crystallizationconditions sources of said oxides and a templating agent comprising aquaternary ammonium cation having the structure

where X— is an anion which is not detrimental to the formation of thecrystalline material.
 8. The method according to claim 7 wherein theoxides are silicon oxide and aluminum oxide.
 9. The method of claim 7wherein the crystalline material has, after calcination, the X-raydiffraction lines of Table I.
 10. A process for converting hydrocarbonscomprising contacting a hydrocarbonaceous feed at hydrocarbon convertingconditions with a catalyst comprising a zeolite having a mole ratio ofabout 20 or greater of an oxide selected from the group consisting ofsilicon oxide, germanium oxide and mixtures thereof to an oxide selectedfrom aluminum oxide, gallium oxide, iron oxide, titanium oxide, indiumoxide, vanadium oxide and mixtures thereof, and having, aftercalcination, the X-ray diffraction lines of Table I.
 11. The process ofclaim 10 wherein the zeolite is predominantly in the hydrogen form. 12.The process of claim 10 wherein the zeolite is substantially free ofacidity.
 13. The process of claim 10 wherein the process is ahydrocracking process comprising contacting the catalyst with ahydrocarbon feedstock under hydrocracking conditions.
 14. The process ofclaim 13 wherein the zeolite is predominantly in the hydrogen form. 15.The process of claim 10 wherein the process is a dewaxing processcomprising contacting the catalyst with a hydrocarbon feedstock underdewaxing conditions.
 16. The process of claim 15 wherein the zeolite ispredominantly in the hydrogen form.
 17. The process of claim 10 whereinthe process is a process for improving the viscosity index of a dewaxedproduct of waxy hydrocarbon feeds comprising contacting the catalystwith a waxy hydrocarbon feed under isomerization dewaxing conditions.18. The process of claim 17 wherein the zeolite is predominantly in thehydrogen form.
 19. The process of claim 10 wherein the process is aprocess for producing a C₂₀₊ lube oil from a C₂₀₊ olefin feed comprisingisomerizing said olefin feed under isomerization conditions over thecatalyst.
 20. The process of claim 19 wherein the zeolite ispredominantly in the hydrogen form.
 21. The process of claim 19 whereinthe catalyst further comprises at least one Group VIII metal.
 22. Theprocess of claim 10 wherein the process is a process for catalyticallydewaxing a hydrocarbon oil feedstock boiling above about 350° F. andcontaining straight chain and slightly branched chain hydrocarbonscomprising contacting said hydrocarbon oil feedstock in the presence ofadded hydrogen gas at a hydrogen pressure of about 15-3000 psi underdewaxing conditions with the catalyst.
 23. The process of claim 22wherein the zeolite is predominantly in the hydrogen form.
 24. Theprocess of claim 22 wherein the catalyst further comprises at least oneGroup VIII metal.
 25. The process of claim 22 wherein said catalystcomprises a layered catalyst comprising a first layer comprising thezeolite and at least one Group VIII metal, and a second layer comprisingan aluminosilicate zeolite which has a different shape selectivity thanthe zeolite of said first layer.
 26. The process of claim 10 wherein theprocess is a process for preparing a lubricating oil which comprises:hydrocracking in a hydrocracking zone a hydrocarbonaceous feedstock toobtain an effluent comprising a hydrocracked oil; and catalyticallydewaxing said effluent comprising hydrocracked oil at a temperature ofat least about 400° F. and at a pressure of from about 15 psig to about3000 psig in the presence of added hydrogen gas with the catalyst. 27.The process of claim 26 wherein the zeolite is predominantly in thehydrogen form.
 28. The process of claim 26 wherein the catalyst furthercomprises at least one Group VIII metal.
 29. The process of claim 10wherein the process is a process for isomerization dewaxing a raffinatecomprising contacting said raffinate in the presence of added hydrogenunder isomerization dewaxing conditions with the catalyst.
 30. Theprocess of claim 29 wherein the zeolite is predominantly in the hydrogenform.
 31. The process of claim 29 wherein the catalyst further comprisesat least one Group VIII metal.
 32. The process of claim 29 wherein theraffinate is bright stock.
 33. The process of claim 10 wherein theprocess is a catalytic cracking process comprising contacting ahydrocarbon feedstock in a reaction zone under catalytic crackingconditions in the absence of added hydrogen with the catalyst.
 34. Theprocess of claim 33 wherein the zeolite is predominantly in the hydrogenform.
 35. The process of claim 33 wherein the catalyst additionallycomprises a large pore crystalline cracking component.
 36. The processof claim 10 wherein the process is a process for oligomerizing olefinscomprising contacting an olefin feed under oligomerization conditionswith the catalyst.
 37. The process of claim 10 wherein the process is aprocess for isomerizing olefins comprising contacting an olefin feedunder isomerization conditions with the catalyst.
 38. The process ofclaim 37 wherein the olefin feed comprises at least one C₄-C₆ normalolefin.
 39. The process of claim 10 wherein the process is a process forthe production of higher molecular weight hydrocarbons from lowermolecular weight hydrocarbons comprising the steps of: (a) introducinginto a reaction zone a lower molecular weight hydrocarbon-containing gasand contacting said gas in said zone under C₂₊ hydrocarbon synthesisconditions with the catalyst and a metal or metal compound capable ofconverting the lower molecular weight hydrocarbon to a higher molecularweight hydrocarbon; and (b) withdrawing from said reaction zone a highermolecular weight hydrocarbon-containing stream.
 40. The process of claim39 wherein the metal or metal compound comprises a lanthanide oractinide metal or metal compound.
 41. The process of claim 39 whereinthe lower molecular weight hydrocarbon is methane.
 42. A process forconverting lower alcohols and other oxygenated hydrocarbons comprisingcontacting said lower alcohol or other oxygenated hydrocarbon underconditions to produce liquid products with a catalyst comprising azeolite having a mole ratio of about 20 or greater of an oxide selectedfrom the group consisting of silicon oxide, germanium oxide and mixturesthereof to an oxide selected from aluminum oxide, gallium oxide, ironoxide, titanium oxide, indium oxide, vanadium oxide and mixturesthereof, and having, after calcination, the X-ray diffraction lines ofTable I.
 43. In a process for the reduction of oxides of nitrogencontained in a gas stream in the presence of oxygen wherein said processcomprises contacting the gas stream with a zeolite, the improvementcomprising using as the zeolite a zeolite having a mole ratio of about20 or greater of an oxide selected from the group consisting of siliconoxide, germanium oxide and mixtures thereof to an oxide selected fromaluminum oxide, gallium oxide, iron oxide, titanium oxide, indium oxide,vanadium oxide and mixtures thereof, and having, after calcination, theX-ray diffraction lines of Table I.
 44. The process of claim 43 whereinsaid zeolite contains a metal or metal ions capable of catalyzing thereduction of the oxides of nitrogen.
 45. The process of claim 44 whereinthe metal is copper, cobalt or mixtures thereof.
 46. The process ofclaim 44 wherein the gas stream is the exhaust stream of an internalcombustion engine.
 47. A process for the separation of nitrogen from anitrogen-containing gas mixture comprising contacting the mixture with acomposition comprising a zeolite having a mole ratio of about 20 orgreater of an oxide selected from the group consisting of silicon oxide,germanium oxide and mixtures thereof to an oxide selected from aluminumoxide, gallium oxide, iron oxide, titanium oxide, indium oxide, vanadiumoxide and mixtures thereof, and having, after calcination, the X-raydiffraction lines of Table I.
 48. The process of claim 47 wherein thegas mixture contains methane.